Functional ethylene and 1,3-diene copolymers

ABSTRACT

The invention relates to a copolymer of ethylene and of a 1,3-diene of formula CH2═CR—CH═CH2, which copolymer bears an amine function, the symbol R representing a hydrocarbon chain having from 3 to 20 carbon atoms. Such a copolymer improves the compromise between the content of ethylene in the polymer, its crystallinity and the stiffness of a rubber composition containing it.

The present invention relates to copolymers of ethylene and of 1,3-diene intended to be used in rubber compositions for tyres.

The most widely used diene copolymers in the manufacture of tyres are polybutadienes, polyisoprenes, in particular natural rubber, and copolymers of 1,3-butadiene and of styrene.

It has been proposed, in particular in document WO 2014114607, to use copolymers of ethylene and of 1,3-butadiene in rubber compositions for tyres. These copolymers are synthesized by copolymerization of ethylene and 1,3-butadiene in the presence of a catalytic system comprising a rare-earth metallocene. The reinforced rubber compositions of ethylene/1,3-butadiene copolymer are in particular described for use in a tread of a tyre. These diene rubber compositions, once crosslinked, exhibit a much higher stiffness than the diene rubber compositions customarily used and may therefore prove unsuitable for certain applications. There is therefore a need to significantly reduce the cured stiffness of such compositions comprising an ethylene-based diene rubber.

The applicant has discovered a copolymer which makes it possible to solve the problems mentioned.

Thus a first subject of the invention is a copolymer of ethylene and of a 1,3-diene of formula (I), which copolymer bears an amine function,

CH₂═CR—CH═CH₂  (I)

the symbol R representing a hydrocarbon chain having from 3 to 20 carbon atoms.

Another subject of the invention is a rubber composition which comprises a copolymer in accordance with the invention, a reinforcing filler and a crosslinking system, which copolymer is an elastomer.

The invention also relates to a tyre which comprises a rubber composition in accordance with the invention.

The invention also relates to a process for preparing a copolymer in accordance with the invention, which process comprises the following steps:

a) the copolymerization of ethylene and of a 1,3-diene of formula (I) in the presence of a catalytic system comprising a metallocene of formula (II) and an organomagnesium compound of formula (III)

CH₂═CR—CH═CH₂  (I),

P(Cp¹Cp²)Nd(BH₄)_((1+y))L_(y)-N_(x)  (II),

MgR¹R²  (III),

the symbol R representing a hydrocarbon chain having from 3 to 20 carbon atoms,

Cp¹ and Cp², which may be identical or different, being selected from the group consisting of the cyclopentadienyl group of formula C₅H₄, the unsubstituted fluorenyl group of formula C₁₃H₈ and substituted fluorenyl groups,

P being a group bridging the two Cp¹ and Cp² groups and representing a ZR³R⁴ group, Z representing a silicon or carbon atom, R³ and R⁴, which are identical or different, each representing an alkyl group comprising from 1 to 20 carbon atoms, preferably a methyl,

y, which is an integer, being equal to or greater than 0,

x, which may or may not be an integer, being equal to or greater than 0,

L representing an alkali metal selected from the group consisting of lithium, sodium and potassium,

N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran,

R¹ and R², which may be identical or different, representing a carbon group,

b) the reaction of a functionalizing agent, compound of formula (IV), with the copolymer obtained in step a),

Si(Fc¹)_(3-g)(Rc²)_(g)(Rca)  (IV)

the Fc¹ symbols, which may be identical or different, representing an alkoxy group or a halogen atom,

the Rc² symbols, which may be identical or different, representing a hydrogen atom or a hydrocarbon chain,

the Rca symbol representing a hydrocarbon chain substituted by an amine function,

g being an integer ranging from 0 to 1,

c) where appropriate, a hydrolysis reaction.

DETAILED DESCRIPTION

Any interval of values denoted by the expression “between a and b” represents the range of values greater than “a” and less than “b” (that is to say limits a and b excluded), whereas any interval of values denoted by the expression “from a to b” means the range of values extending from “a” up to “b” (that is to say including the strict limits a and b). The abbreviation “phr” means parts by weight per hundred parts by weight of elastomer (of the total of the elastomers if several elastomers are present).

The expression “based on” used to define the constituents of a catalytic system or of a composition is understood to mean the mixture of these constituents, or the product of the reaction of a portion or of all of these constituents with one another.

Unless otherwise indicated, the contents of the units resulting from the insertion of a monomer into a copolymer are expressed as molar percentage relative to all of the monomer units of the copolymer.

The compounds mentioned in the description can be of fossil origin or be biobased. In the latter case, they may be partially or completely derived from biomass or be obtained from renewable starting materials derived from biomass. Elastomers, plasticizers, fillers and the like are notably concerned.

Since the 1,3-diene of formula (I) as defined above and which is useful for the purposes of the invention is a substituted 1,3-diene, the 1,3-diene can give rise to units of 1,2 configuration represented by the formula (1), of 3,4 configuration represented by the formula (2) and of 1,4 configuration, the trans form of which is represented below by the formula (3).

As is also well known, the ethylene unit is a unit of —(CH₂—CH₂)— moiety.

Since the copolymer which is useful for the purposes of the invention is a copolymer of ethylene and of the 1,3-diene, the monomer units of the copolymer are therefore units resulting from the polymerization of ethylene and of the 1,3-diene. The copolymer thus comprises ethylene units and units of the 1,3-diene. According to any one of the embodiments of the invention, the 1,3-diene is just one compound, that is to say just one 1,3-diene of formula (I), or is a mixture of 1,3-dienes of formula (I), the 1,3-dienes of the mixture differing from one another by the group represented by the symbol R. The copolymer which is useful for the purposes of the invention is advantageously a statistical copolymer according to any one of the embodiments of the invention.

Preferably, the copolymer contains ethylene units which represent more than 50 mol % of the monomer units of the copolymer, that is to say more than 50 mol % of the ethylene units and the 1,3-diene units. Very preferentially, the copolymer contains ethylene units which represent at least 60 mol % of the monomer units of the copolymer. More preferentially, the copolymer contains ethylene units which represent at least 70 mol % of the monomer units of the copolymer. In other words, the copolymer preferentially contains more than 50 mol % of ethylene units, more preferentially at least 60 mol % of ethylene units, even more preferentially at least 70 mol % of ethylene units.

Preferably, the copolymer contains at most 90 mol % of ethylene units, in which case the ethylene units in the copolymer represent at most 90 mol % of the monomer units of the copolymer.

According to a particular embodiment of the invention, the copolymer contains at most 85 mol % of ethylene units, in which case the ethylene units in the copolymer represent at most 85 mol % of the monomer units of the copolymer.

According to one preferential embodiment of the invention, in the copolymer in accordance with the invention, the ethylene units represent from 60 to 90 mol % of the monomer units of the copolymer, advantageously from 70 to 90 mol % of the monomer units of the copolymer.

According to another particular embodiment of the invention, in the copolymer in accordance with the invention, the ethylene units represent from 60 to 85 mol % of the monomer units of the copolymer, advantageously from 70 to 85 mol % of the monomer units of the copolymer.

In formula (I) of the 1,3-diene, the hydrocarbon chain represented by the symbol R is a hydrocarbon chain of from 3 to 20 carbon atoms. Preferably, the symbol R represents a hydrocarbon chain having from 6 to 16 carbon atoms.

The hydrocarbon chain represented by the symbol R may be a saturated or unsaturated chain. Preferably, the symbol R represents an aliphatic chain. It may be a linear or branched chain, in which case the symbol R represents a linear or branched chain. Preferably, the hydrocarbon chain is acyclic, in which case the symbol R represents an acyclic chain. Better still, the symbol R represents an unsaturated and branched acyclic hydrocarbon chain. The hydrocarbon chain represented by the symbol R is advantageously an unsaturated and branched acyclic chain containing from 3 to 20 carbon atoms, in particular from 6 to 16 carbon atoms. Very advantageously, the 1,3-diene is myrcene or β-farnesene.

According to one preferential embodiment of the invention, the 1,3-diene is myrcene.

According to another preferential embodiment of the invention, the 1,3-diene is β-farnesene.

Preferably, the copolymer of ethylene and of the 1,3-diene has a glass transition temperature below −35° C., preferably between −90° C. and −35° C.

According to a first variant of the invention, the copolymer contains units of the 1,3-diene of 1,2 or 3,4 configuration, the group consisting of units of the 1,3-diene of 1,2 configuration and units of the 1,3-diene of 3,4 configuration representing more than 50 mol % of the units of the 1,3-diene. In other words, according to this first variant, the units of the 1,3-diene in the copolymer contain more than 50 mol % of the units of 1,2 configuration or of 3,4 configuration. In this variant, the balance to 100 mol % of the units of the 1,3-diene in the copolymer is completely or partially formed of units of the 1,3-diene of 1,4 configuration. According to this first variant, preferentially more than half of the units of the 1,3-diene of 1,4 configuration are of trans-1,4 configuration, more preferentially all the units of the 1,3-diene of 1,4 configuration are of trans-1,4 configuration.

According to a second variant of the invention, the copolymer contains units of the 1,3-diene which are more than 50% of 1,4 configuration. In other words, the units of the 1,3-diene of 1,4 configuration represent more than 50 mol % of the units of the 1,3-diene. In this variant, the balance to 100 mol % of the units of the 1,3-diene in the copolymer is completely or partially formed of units of the 1,3-diene of 1,2 or 3,4 configuration. Preferably, the units of the 1,3-diene of 1,4 configuration represent more than 70 mol % of the units of the 1,3-diene. Advantageously, more than half of the units of the 1,3-diene of 1,4 configuration are of trans-1,4 configuration, which means that the units of the 1,3-diene of trans-1,4 configuration represent more than 50 mol % of the units of the 1,3-diene of 1,4 configuration.

The amine function borne by the copolymer is a protected or unprotected primary amine function, a protected or unprotected secondary amine function or a tertiary amine function. The protective group for the amine functions is for example a silyl group, in particular a trimethylsilyl or tert-butyldimethylsilyl group.

As is well known, the primary amine function borne by the copolymer has the formula —NH₂, the secondary amine function has the formula —NHR_(A), the tertiary amine function has the formula —N(R_(A))₂, the symbols R_(A), which may be identical or different, each representing a hydrocarbon chain. In the case of the tertiary amine function, the two R_(A) can be linked to form a ring.

Preferably, the amine function borne by the copolymer is a tertiary amine function. Advantageously, the amine function borne by the copolymer is a tertiary amine of formula —N(R_(A))₂ in which each R_(A) represents an alkyl, preferentially a methyl or an ethyl.

According to a particularly preferred embodiment of the invention, the copolymer further bears a second function other than an amine function. The second function borne by the copolymer is preferably a silanol function or an alkoxysilane function.

According to a first variant of the particular embodiment in which the copolymer bears a second function, the copolymer bears a functional group of formula (III-a)

Si(OR′)_(2-f)(R″)_(f)(Ra″)  (III-a)

the R′ symbols, which may be identical or different, representing an alkyl,

the R″ symbols, which may be identical or different, representing a hydrogen atom or a hydrocarbon chain,

the Ra″ symbol representing a hydrocarbon chain substituted by an amine function,

f being an integer ranging from 0 to 1.

According to this first variant, the second function is an alkoxysilane function. In the formula (III-a), the R′ symbols are preferentially an alkyl having at most 6 carbon atoms, more preferentially a methyl or an ethyl, more preferentially still a methyl. The R″ symbols are advantageously methyl or ethyl, more particularly methyl.

According to a second variant of the particular embodiment in which the copolymer bears a second function, the copolymer bears a functional group of formula (III-b)

Si(OH)(R″)(Ra″)  (III-b)

the R″ symbol representing a hydrogen atom or a hydrocarbon chain,

the Ra″ symbol representing a hydrocarbon chain substituted by an amine function.

According to this second variant, the second function is a silanol function.

Among the hydrocarbon chains represented by the R″ symbols in formulae (III-a) and (III-b), mention may be made of alkyls, in particular those having 1 to 6 carbon atoms, preferentially methyl or ethyl, more preferentially methyl. Preferably, the symbols R″, which may be identical or different, represent an alkyl having at most 6 carbon atoms in the formulae (III-a) and (III-b).

Mention may be made, as a functional group borne by the copolymer and comprising an amine function and an alkoxysilane function, of the 3-(N,N-dimethylamino)propyldimethoxysilyl, 3-(N,N-dimethylamino)propyldiethoxysilyl, 3-aminopropyldimethoxysilyl, 3-aminopropyldiethoxysilyl, 3-(N,N-dimethylamino)propylmethoxymethylsilyl, 3-(N,N-dimethylamino)propylmethoxyethylsilyl, 3-(N,N-dimethylamino)propylethoxymethylsilyl, 3-(N,N-dimethylamino)propylethoxyethylsilyl, 3-aminopropylmethoxymethylsilyl, 3-aminopropylmethoxyethylsilyl, 3-aminopropylethoxymethylsilyl and 3-aminopropylethoxyethylsilyl groups.

Mention may also be made, as a functional group borne by the copolymer and comprising an amine function and a silanol function, of the silanol form of the functional groups mentioned above which contain one and only one ethoxy or methoxy function, it being possible for the silanol form to be obtained by hydrolysis of the ethoxy or methoxy function. In this regard, the 3-(N,N-dimethylamino)propylmethylsilanol, 3-(N,N-dimethylamino)propylethylsilanol, 3-aminopropylmethylsilanol and 3-aminopropylethylsilanol groups are suitable.

According to a very preferential embodiment of the invention, the functional group borne by the copolymer and comprising an amine and alkoxysilane function is of formula (III-a) in which f is equal to 0. According to this very preferential embodiment, the groups for which R′ is a methyl or an ethyl, such as for example the 3-(N,N-dimethylamino)propyldimethoxysilyl, 3-(N,N-dimethylamino)propyldiethoxysilyl, 3-aminopropyldimethoxysilyl and 3-aminopropyldiethoxysilyl groups, are very particularly suitable. Also suitable are the protected forms of the amine function of the functional groups mentioned in the preceding list, protected by a silyl group, in particular a trimethylsilyl or tert-butyldimethylsilyl group.

According to one even more preferential embodiment of the invention, the functional group borne by the copolymer and comprising an amine and alkoxysilane function is of formula (III-a) in which f is equal to 0 and R′ is a methyl. According to this even more preferential embodiment, the 3-(N,N-dimethylamino)propyldimethoxysilyl and 3-aminopropyldimethoxysilyl groups, and also the protected forms of the amine function of 3-aminopropyldimethoxysilyl, protected by a trimethylsilyl or a tert-butyldimethylsilyl, are very particularly suitable.

The copolymer can be prepared by a process which comprises a step a) and a step b). Step a) is the copolymerization of ethylene and of the 1,3-diene which is useful for the purposes of the invention in the presence of a catalytic system comprising a metallocene of formula (II) and an organomagnesium compound of formula (III)

P(Cp¹Cp²)Nd(BH₄)_((1+y))L_(y)-N_(x)  (II)

MgR¹R²  (III)

Cp¹ and Cp², which may be identical or different, being selected from the group consisting of the cyclopentadienyl group of formula C₅H₄, the unsubstituted fluorenyl group of formula C₁₃H₈ and substituted fluorenyl groups,

P being a group bridging the two Cp¹ and Cp² groups and representing a ZR³R⁴ group, Z representing a silicon or carbon atom, R³ and R⁴, which are identical or different, each representing an alkyl group comprising from 1 to 20 carbon atoms, preferably a methyl,

y, which is an integer, being equal to or greater than 0,

x, which may or may not be an integer, being equal to or greater than 0,

L representing an alkali metal selected from the group consisting of lithium, sodium and potassium,

N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran,

R¹ and R², which may be identical or different, representing a carbon group.

Mention may be made, as substituted fluorenyl groups, of those substituted by alkyl radicals having from 1 to 6 carbon atoms or by aryl radicals having from 6 to 12 carbon atoms. The choice of the radicals is also guided by the accessibility to the corresponding molecules, which are the substituted fluorenes, because the latter are commercially available or can be easily synthesized.

Mention may more particularly be made, as substituted fluorenyl groups, of the 2,7-di(tert-butyl)fluorenyl and 3,6-di(tert-butyl)fluorenyl groups. The 2, 3, 6 and 7 positions respectively denote the positions of the carbon atoms of the rings as represented in the diagram below, the 9 position corresponding to the carbon atom to which the bridge P is attached.

The group P bridging the two Cp¹ and Cp¹ groups preferably denotes the SiMe₂ group.

The catalytic system can be prepared conventionally by a process analogous to that described in patent application WO 2007054224 or WO 2007054223. For example, the organomagnesium compound and the metallocene are reacted in a hydrocarbon solvent typically at a temperature ranging from 20° C. to 80° C. for a period of time of between 5 and 60 minutes. The catalytic system is generally prepared in an aliphatic hydrocarbon solvent, such as methylcyclohexane, or an aromatic hydrocarbon solvent, such as toluene. Generally, after its synthesis, the catalytic system is used in this form in the process for the synthesis of the copolymer in accordance with the invention.

Alternatively, the catalytic system can be prepared by a process analogous to that described in patent application WO 2017093654 A1 or in patent application WO 2018020122 A1. According to this alternative, the catalytic system further contains a preformation monomer chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene, in which case the catalytic system is based at least on the metallocene, the organomagnesium compound and the preformation monomer. For example, the organomagnesium compound and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature of from 20° C. to 80° C. for 10 to 20 minutes to obtain a first reaction product, then the preformation monomer, chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene, is reacted with this first reaction product at a temperature ranging from 40° C. to 90° C. for 1 h to 12 h. The catalytic system thus obtained can be used immediately in the process in accordance with the invention or be stored under an inert atmosphere before the use thereof in the process in accordance with the invention.

The metallocene used for preparing the catalytic system can be in the form of a crystalline or non-crystalline powder, or else in the form of single crystals. The metallocene can be provided in a monomer or dimer form, these forms depending on the method of preparation of the metallocene, as for example is described in patent application WO 2007054224 or WO 2007054223. The metallocene can be prepared conventionally by a process analogous to that described in patent application WO 2007054224 or WO 2007054223, in particular by reaction, under inert and anhydrous conditions, of the salt of an alkali metal of the ligand with a rare earth metal borohydride, in a suitable solvent, such as an ether, for example diethyl ether or tetrahydrofuran, or any other solvent known to a person skilled in the art. After reaction, the metallocene is separated from the reaction byproducts by techniques known to a person skilled in the art, such as filtration or precipitation from a second solvent. In the end, the metallocene is dried and isolated in the solid form.

Like any synthesis carried out in the presence of an organometallic compound, the synthesis of the metallocene and that of the catalytic system take place under anhydrous conditions under an inert atmosphere. Typically, the reactions are carried out starting from anhydrous solvents and compounds under anhydrous nitrogen or argon.

The organomagnesium compound of use for the requirements of the invention is of formula MgR¹R² in which R¹ and R², which may be identical or different, represent a carbon group. Carbon group is understood to mean a group which contains one or more carbon atoms. Preferably, R¹ and R² contain from 2 to 10 carbon atoms. More preferentially, R¹ and R² each represent an alkyl. The organomagnesium compound is advantageously a dialkylmagnesium compound, better still butylethylmagnesium or butyloctylmagnesium, even better still butyloctylmagnesium.

According to any one of the embodiments of the invention, the molar ratio of the organomagnesium compound to the metal Nd constituting the metallocene is preferably within a range extending from 1 to 100, more preferably is greater than or equal to 1 and less than 10. The range of values extending from 1 to less than 10 is in particular more favourable for obtaining copolymers of high molar masses.

When the copolymer useful for the purposes of the invention is a copolymer which has a microstructure as defined according to the first variant of the invention, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp¹ and Cp², which may be identical or different, are selected from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C₁₃H₈. For this variant, the metallocenes of the following formulae, in which the symbol Flu presents the fluorenyl group of formula C₁₃H₈, are particularly suitable: [{Me₂SiFlu₂Nd(μ-BH₄)₂Li(THF)}₂]; [Me₂SiFlu₂Nd(μ-BH₄)₂Li(THF)]; [Me₂SiFlu₂Nd(μ-BH₄)(THF)]; [{Me₂SiFlu₂Nd(μ-BH₄)(THF)}₂]; [Me₂SiFlu₂Nd(μ-BH₄)].

When the copolymer useful for the purposes of the invention is a copolymer which has a microstructure as defined according to the second variant of the invention, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp¹ denotes a cyclopentadienyl group Cp of formula C₅H₄ and Cp² denotes a fluorenyl group Flu of formula C₁₃H₈.

Those skilled in the art also adapt the polymerization conditions and the concentrations of each of the reactants (constituents of the catalytic system, monomers) according to the equipment (tools, reactors) used to carry out the polymerization and the various chemical reactions. As is known to those skilled in the art, the copolymerization and also the handling of the monomers, of the catalytic system and of the polymerization solvent(s) take place under anhydrous conditions and under an inert atmosphere. The polymerization solvents are typically aliphatic or aromatic hydrocarbon solvents.

The polymerization is preferably carried out in solution, continuously or batchwise. The polymerization solvent can be an aromatic or aliphatic hydrocarbon solvent. Mention may be made, as examples of polymerization solvent, of toluene and methylcyclohexane. The monomers can be introduced into the reactor containing the polymerization solvent and the catalytic system or, conversely, the catalytic system can be introduced into the reactor containing the polymerization solvent and the monomers. The copolymerization is typically carried out under anhydrous conditions and in the absence of oxygen, in the optional presence of an inert gas. The polymerization temperature generally varies within a range extending from 30 to 150° C., preferentially from 30 to 120° C. Preferably, the copolymerization is carried out at constant ethylene pressure.

During the polymerization of ethylene and the 1,3-diene in a polymerization reactor, ethylene and the 1,3-diene can be added continuously to the polymerization reactor, in which case the polymerization reactor is a fed reactor. This embodiment is very particularly suitable for the synthesis of a statistical copolymer.

Step b) consists in reacting a functionalizing agent with the copolymer obtained in step a) in order to functionalize the copolymer. The functionalizing agent is a compound of formula (IV),

Si(Fc¹)_(3-g)(Rc²)_(g)(Rca)  (IV)

the Fc¹ symbols, which may be identical or different, representing an alkoxy group or a halogen atom,

the Rc² symbols, which may be identical or different, representing a hydrogen atom or a hydrocarbon chain,

the Rca symbol representing a hydrocarbon chain substituted by an amine function,

g being an integer ranging from 0 to 1.

The alkoxy group represented by the Fc¹ symbol is preferably methoxy or ethoxy.

According to one preferential embodiment of the invention, the functionalizing agent contains at least one Fc¹ symbol, in particular methoxy or ethoxy. Advantageously, the functionalizing agent is then of formula (IV-1)

MeOSi(Fc¹)_(2-g)(Rc²)_(g)(Rca)  (IV-1)

the Fc¹, Rc² and Rca symbols and g being as defined in the formula (IV).

According to a more preferential embodiment, the functionalizing agent contains at least two Fc¹ symbols, in particular methoxy or ethoxy. Advantageously, the functionalizing agent is then of formula (IV-2)

(MeO)₂Si(Fc¹)_(1-g)(Rc²)_(g)(Rca)  (IV-2)

the Fc¹, Rc² and Rca symbols and g being as defined in the formula (IV).

According to an even more preferential embodiment, the functionalizing agent contains at least three Fc¹ symbols, in particular methoxy or ethoxy. Advantageously, the functionalizing agent is then of formula (IV-3)

(MeO)₃Si(Rca)  (IV-3)

the Rca symbol being as defined in the formula (IV).

Among the hydrocarbon chains represented by the Rc² symbols in formulae (IV), (IV-1), (IV-2), mention may be made of alkyls, preferably alkyls having at most 6 carbon atoms, more preferentially methyl or ethyl, better still methyl.

Among the hydrocarbon chains denoted in the Rca symbol in formulae (IV), (IV-1), (IV-2), (IV-3), mention may be made of alkanediyl chains, preferably those comprising at most 6 carbon atoms, such as the 1,3-propanediyl group.

The amine function denoted in the Rca symbol, namely the amine function of the functionalizing agent, is a protected primary amine function, a protected secondary amine function or a tertiary amine function. As protective groups for the primary amine and secondary amine functions, mention may be made of silyl groups, for example the trimethylsilyl and tert-butyldimethylsilyl groups. Preferably, the amine function of the functionalizing agent is a tertiary amine function. Advantageously, the amine function of the functionalizing agent is a tertiary amine of formula —N(R_(B))₂ in which each R_(B) represents an alkyl, preferentially a methyl or an ethyl.

Mention may be made, as functionalizing agent, of the compounds (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)methyldiethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldiethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N,N-dimethylaminopropyl)triethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, (N-(3-triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, preferably (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane and (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, more preferentially (N,N-dimethylaminopropyl)trimethoxysilane and (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine.

The functionalizing agent is typically added to the polymerization medium resulting from step a). It is typically added to the polymerization medium at a degree of conversion of the monomers selected by those skilled in the art depending on the desired macrostructure of the copolymer. Since step a) is generally carried out under ethylene pressure, a degassing of the polymerization reactor may be carried out before the addition of the functionalizing agent. The functionalizing agent is added under inert and anhydrous conditions to the polymerization medium, maintained at the polymerization temperature. Use is typically made of from 0.25 to 10 mol of functionalizing agent per 1 mol of cocatalyst, preferably of from 2 to 4 mol of functionalizing agent per 1 mol of cocatalyst.

The functionalizing agent is brought into contact with the polymerization medium for a time sufficient to enable the functionalization reaction. This contact time is judiciously selected by those skilled in the art as a function of the concentration of the reaction medium and of the temperature of the reaction medium. Typically, the functionalization reaction is carried out under stirring, at a temperature ranging from 17° C. to 80° C., for 0.01 to 24 hours.

Once functionalized, the copolymer may be recovered, in particular by isolating it from the reaction medium. The techniques for separating the copolymer from the reaction medium are well known to those skilled in the art and are selected by those skilled in the art depending on the amount of copolymer to be separated, its macrostructure and the tools available to those skilled in the art. Mention may be made, for example, of the techniques of coagulating the copolymer in a solvent such as methanol, the techniques of evaporating the solvent of the reaction medium and the residual monomers, for example under reduced pressure.

When the functionalizing agent is of formula (IV), (IV-1) or (IV-2) and g is equal to 1, step b) may be followed by a hydrolysis reaction in order to form a copolymer bearing a silanol function. The hydrolysis may be carried out by a step of stripping of the solution containing the copolymer at the end of step b), in a manner known to those skilled in the art.

When the functionalizing agent is of formula (IV), (IV-1), (IV-2) or (IV-3), and comprises a primary or secondary amine function in a protected form, step b) may also be followed by a hydrolysis reaction in order to deprotect the function. The hydrolysis reaction, step of deprotecting the function, is generally carried out in an acid or basic medium. For example, a silyl group, in particular a trimethylsilyl or tert-butyldimethylsilyl group, which protects an amine function may be hydrolysed in an acid or basic medium in a manner known to those skilled in the art. The choice of the deprotection conditions is judiciously made by those skilled in the art taking into account the chemical structure of the substrate to be deprotected.

Step c) of the process in accordance with the invention is an optional step depending on whether or not it is desired to convert the alkoxysilane group into a silanol group or whether or not it is desired to deprotect the protected function. Preferentially, step c) is carried out before separating the copolymer from the reaction medium at the end of step b) or else at the same time as this separation step.

According to any one of the embodiments of the invention, the amine function borne by the copolymer in accordance with the invention is preferentially at the chain end of the copolymer.

The copolymer in accordance with the invention, described according to any one of the embodiments of the invention, including in the preferential variants thereof, exhibits both a lower stiffness and a lower crystallinity than a copolymer of ethylene and 1,3-butadiene which has however the same ethylene content. The substitution in a rubber composition of the copolymer in accordance with the invention for a copolymer of ethylene and 1,3-butadiene which has however the same ethylene content makes it possible to give a rubber composition a lower stiffness. In addition, the functionalization of the copolymer with an amine function makes it possible to improve the interaction between the copolymer and a reinforcing filler, in particular a carbon black or a silica or a mixture thereof, which helps to improve the mechanical properties of the copolymer and consequently the mechanical properties of the rubber composition containing a copolymer in accordance with the invention and reinforced with a reinforcing filler. The copolymer in accordance with the invention is advantageously an elastomer, hereinafter referred to as a diene and ethylene elastomer. It is in particular intended to be used in a rubber composition, in particular for tyres.

The rubber composition, another subject of the invention, therefore has the essential feature of comprising a diene and ethylene elastomer in accordance with the invention.

Preferably, the rubber composition contains more than 50 phr of the diene and ethylene elastomer, more preferentially at least 80 phr of the diene and ethylene elastomer. The balance to 100 phr may consist wholly or partly of a diene and ethylene elastomer devoid of a silanol function or of an alkoxysilane function. The rubber composition may also comprise an elastomer selected from the group of diene elastomers consisting of polybutadienes, polyisoprenes, butadiene copolymers, isoprene copolymers and a mixture thereof. Advantageously, the content of the diene and ethylene elastomer in accordance with the invention is 100 phr. The diene and ethylene elastomer may consist of a mixture of diene and ethylene elastomers which differ from each other by virtue of their microstructures or their macrostructures.

Another essential feature of the rubber composition is that it comprises, in addition to the diene and ethylene elastomer, a reinforcing filler. Use may be made of any type of “reinforcing” filler known for its abilities to reinforce a rubber composition which can be used in particular in the manufacture of tyres, for example an organic filler, such as carbon black, an inorganic filler, such as silica, or else a mixture of these two types of fillers.

According to one embodiment of the invention, the reinforcing filler comprises a carbon black.

According to another particular embodiment of the invention, the reinforcing filler comprises a silica.

According to yet another embodiment of the invention, the reinforcing filler comprises a carbon black and a silica.

According to any one of the embodiments of the invention, the reinforcing filler preferably comprises a carbon black and a silica.

All carbon blacks, in particular blacks of the HAF, ISAF, SAF, FF, FEF, GPF and SRF type, conventionally used in rubber compositions for tyres (“tyre-grade” blacks) are suitable as carbon blacks. These carbon blacks can be used in the isolated state, as available commercially, or in any other form, for example as support for some of the rubber additives used.

The term “reinforcing inorganic filler” should be understood, in the present patent application, by definition, to mean any inorganic or mineral filler, whatever its colour and its origin (natural or synthetic), also referred to as “white filler”, “clear filler”, indeed even “non-black filler”, in contrast to carbon black, capable of reinforcing, by itself alone, without means other than an intermediate coupling agent, a rubber composition intended for the manufacture of tyres, in other words capable of replacing, in its reinforcing role, a conventional tyre-grade carbon black; such a filler is generally characterized, in a known way, by the presence of hydroxyl (—OH) groups at its surface.

Mineral fillers of the siliceous type, preferentially silica (SiO₂), are suitable in particular as reinforcing inorganic fillers. The silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica exhibiting a BET specific surface area and also a CTAB specific surface area both of less than 450 m²/g, preferably from 30 to 400 m²/g, in particular between 60 and 300 m²/g. Mention will be made, as highly dispersible precipitated silicas (“HDSs”), for example, of the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia, the Hi-Sil EZ150G silica from PPG, the Zeopol 8715, 8745 and 8755 silicas from Huber or the silicas with a high specific surface area as described in application WO 03/016387.

In the present account, the BET specific surface area is determined in a known way by gas adsorption using the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938, more specifically according to French Standard NF ISO 9277 of December 1996 (multipoint (5 point) volumetric method—gas: nitrogen—degassing: 1 hour at 160° C.—relative pressure p/p₀ range: 0.05 to 0.17). The CTAB specific surface area is the external surface area determined according to French Standard NF T 45-007 of November 1987 (method B).

The physical state under which the reinforcing inorganic filler is provided is not important, whether in the form of a powder, of micropearls, of granules or else of beads. Of course, reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas as described above.

Those skilled in the art will understand that use might be made, as filler equivalent to the reinforcing inorganic filler described in the present section, of a reinforcing filler of another nature, in particular organic nature, such as carbon black, provided that this reinforcing filler is covered with an inorganic layer, such as silica, or else includes, at its surface, functional sites, especially hydroxyl sites, requiring the use of a coupling agent in order to establish the bond between the filler and the elastomer. By way of example, mention may be made, for example, of carbon blacks for tyres, as described, for example, in patent documents WO 96/37547 and WO 99/28380.

Preferentially, the content of reinforcing filler is between 30 and 200 phr, more preferentially between 40 and 160 phr. Any one of these ranges of content of reinforcing filler can apply to any one of the embodiments of the invention.

In order to couple the reinforcing inorganic filler to the elastomer, use is made, in a well-known way, of an at least bifunctional coupling agent, in particular a silane, (or bonding agent) intended to provide a satisfactory connection between the inorganic filler (surface of its particles) and the elastomer. Use is made in particular of organosilanes or polyorganosiloxanes which are at least bifunctional.

Use is made especially of silane polysulfides, referred to as “symmetrical” or “asymmetrical” depending on their specific structure, such as described, for example, in applications WO 03/002648 (or US 2005/016651) and WO 03/002649 (or US 2005/016650).

Particularly suitable, without the definition below being limiting, are silane polysulfides corresponding to the general formula (V):

Z-G-S_(x)-G-Z  (V)

in which:

-   -   x is an integer from 2 to 8 (preferably from 2 to 5);     -   the G symbols, which may be identical or different, represent a         divalent hydrocarbon radical (preferably a C₁-C₁₈ alkylene group         or a C₆-C₁₂ arylene group, more particularly a C₁-C₁₀,         especially C₁-C₄, alkylene, in particular propylene);     -   the Z symbols, which may be identical or different, correspond         to one of the three formulae below:

in which:

-   -   the R^(a) radicals, which are substituted or unsubstituted and         identical to or different from one another, represent a C₁-C₁₈         alkyl, C₅-C₁₈ cycloalkyl or C₆-C₁₈ aryl group (preferably C₁-C₆         alkyl, cyclohexyl or phenyl groups, in particular C₁-C₄ alkyl         groups, more particularly methyl and/or ethyl);     -   the R^(b) radicals, which are substituted or unsubstituted and         identical to or different from one another, represent a C₁-C₁₈         alkoxyl or C₅-C₁₈ cycloalkoxyl group (preferably a group         selected from C₁-C₈ alkoxyls and C₅-C₈ cycloalkoxyls, more         preferentially still a group selected from C₁-C₄ alkoxyls, in         particular methoxyl and ethoxyl).

In the case of a mixture of alkoxysilane polysulfides corresponding to the above formula (I), especially customary commercially available mixtures, the mean value of “x” is a fractional number preferably of between 2 and 5, more preferentially close to 4. However, the invention may also be advantageously performed, for example, with alkoxysilane disulfides (x=2).

Mention will more particularly be made, as examples of silane polysulfides, of bis((C₁-C₄)alkoxyl(C₁-C₄)alkylsilyl(C₁-C₄)alkyl) polysulfides (in particular disulfides, trisulfides or tetrasulfides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides. Use is made in particular, among these compounds, of bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated to TESPT, of formula [(C₂H₅O)₃Si(CH₂)₃S₂]₂, or bis(3-triethoxysilylpropyl) disulfide, abbreviated to TESPD, of formula [(C₂H₅O)₃Si(CH₂)₃S]₂.

Mention will in particular be made, as coupling agent other than alkoxysilane polysulfide, of bifunctional POSs (polyorganosiloxanes) or else of hydroxysilane polysulfides, such as described in patent applications WO 02/30939 (or U.S. Pat. No. 6,774,255) and WO 02/31041 (or US 2004/051210), or else of silanes or POSs bearing azodicarbonyl functional groups, such as described, for example, in patent applications WO 2006/125532, WO 2006/125533 and WO 2006/125534.

The content of coupling agent is advantageously less than 30 phr, it being understood that it is generally desirable to use as little as possible thereof. Typically, the content of coupling agent represents from 0.5% to 15% by weight, relative to the amount of inorganic filler. Its content is preferentially between 0.5 and 16 phr, more preferentially within a range of from 3 to 10 phr. This content is easily adjusted by those skilled in the art according to the content of inorganic filler used in the composition.

The rubber composition in accordance with the invention may also contain, in addition to the coupling agents, coupling activators, agents for covering the inorganic fillers or more generally processing aids that are capable, in a known manner, by means of improving the dispersion of the filler in the rubber matrix and of lowering the viscosity of the compositions, of improving their ability to be processed in the uncured state.

The rubber composition comprises a crosslinking system. The chemical crosslinking enables the formation of covalent bonds between the elastomer chains. The crosslinking system may be a vulcanization system or one or more peroxide compounds, preferably a vulcanization system.

The vulcanization system proper is based on sulfur (or on a sulfur donor) and on a primary vulcanization accelerator. Additional to this base vulcanization system are various known secondary vulcanization accelerators or vulcanization activators, such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (in particular diphenylguanidine), incorporated during the first non-productive phase and/or during the productive phase, as described subsequently. The sulfur is used at a preferential content of 0.5 to 12 phr, in particular of 1 to 10 phr. The primary vulcanization accelerator is used at a preferential content of between 0.5 and 10 phr, more preferentially of between 0.5 and 5 phr. Use may be made, as (primary or secondary) accelerator, of any compound that is capable of acting as accelerator of the vulcanization of diene elastomers in the presence of sulfur, notably accelerators of the thiazole type and also derivatives thereof, or accelerators of thiuram or zinc dithiocarbamate type. Preferably, use is made of a primary accelerator of the sulfenamide type.

When the chemical crosslinking is carried out using one or more peroxide compounds, said peroxide compound or compounds preferably represent from 0.01 to 10 phr. Mention may be made, as peroxide compounds which can be used as chemical crosslinking system, of acyl peroxides, for example benzoyl peroxide or p-chlorobenzoyl peroxide, ketone peroxides, for example methyl ethyl ketone peroxide, peroxyesters, for example t-butyl peroxyacetate, t-butyl peroxybenzoate and t-butyl peroxyphthalate, alkyl peroxides, for example dicumyl peroxide, di(t-butyl) peroxybenzoate and 1,3-bis(t-butylperoxyisopropyl)benzene, or hydroperoxides, for example t-butyl hydroperoxide.

The rubber composition in accordance with the invention may also comprise all or some of the usual additives normally used in elastomer compositions intended to constitute external mixtures of finished rubber articles, such as tyres, in particular treads, such as for example plasticizers or extender oils, whether these are aromatic or non-aromatic in nature, in particular very weakly aromatic or non-aromatic oils (e.g., paraffinic or hydrogenated naphthenic oils, or MES or TDAE oils), vegetable oils, in particular glycerol esters such as glyceryl trioleates, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants or antioxidants.

The rubber composition according to the invention can be manufactured in appropriate mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of thermomechanical working or kneading (sometimes referred to as “non-productive” phase) at high temperature, up to a maximum temperature of between 130° C. and 200° C., preferably between 145° C. and 185° C., followed by a second phase of mechanical working (sometimes referred to as “productive” phase) at lower temperature, typically below 120° C., for example between 60° C. and 100° C., during which finishing phase the chemical crosslinking agent, in particular the vulcanization system, is incorporated.

Generally, all the base constituents of the composition included in the tyre of the invention, with the exception of the crosslinking system, namely the reinforcing inorganic filler and the coupling agent, if appropriate, are intimately incorporated, by kneading, into the elastomer during the first “non-productive” phase, that is to say that at least these various base constituents are introduced into the mixer and are thermomechanically kneaded, in one or more steps, until the maximum temperature of between 130° C. and 200° C., preferably of between 145° C. and 185° C., is reached.

By way of example, the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the optional supplementary processing aids and various other additives, with the exception of the chemical crosslinking agent, are introduced into an appropriate mixer, such as a standard internal mixer. The total duration of the kneading, in this non-productive phase, is preferably between 1 and 15 min. After cooling the mixture thus obtained during the first non-productive phase, the crosslinking system is then incorporated at low temperature, generally in an external mixer, such as an open mill; everything is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.

The final composition thus obtained is subsequently calendered, for example in the form of a sheet or a slab, especially for laboratory characterization, or else extruded in the form of a rubber profiled element which can be used as semi-finished tyre product for a vehicle.

Thus, according to a specific embodiment of the invention, the rubber composition in accordance with the invention, which can either be in the uncured state (before crosslinking or vulcanization) or in the cured state (after crosslinking or vulcanization), is a semi-finished product which may be used in a tyre, especially as a tyre tread.

In summary, the invention is advantageously implemented according to any one of the following embodiments 1 to 39:

Embodiment 1: Copolymer of ethylene and of a 1,3-diene of formula (I), which copolymer bears an amine function,

CH₂═CR—CH═CH₂  (I)

the symbol R representing a hydrocarbon chain having from 3 to 20 carbon atoms.

Embodiment 2: Copolymer according to embodiment 1, in which the amine function is at the chain end of the copolymer.

Embodiment 3: Copolymer according to either one of embodiments 1 and 2, which copolymer is a statistical copolymer.

Embodiment 4: Copolymer according to any one of embodiments 1 to 3, which copolymer contains more than 50 mol % of ethylene units.

Embodiment 5: Copolymer according to any one of embodiments 1 to 4, which copolymer contains at least 60 mol % of ethylene units.

Embodiment 6: Copolymer according to any one of embodiments 1 to 5, which copolymer contains at least 70 mol % of ethylene units.

Embodiment 7: Copolymer according to any one of embodiments 1 to 6, which copolymer contains at most 90 mol % of ethylene units.

Embodiment 8: Copolymer according to any one of embodiments 1 to 6, which copolymer contains at most 85 mol % of ethylene units.

Embodiment 9: Copolymer according to any one of embodiments 1 to 8, which copolymer contains units of the 1,3-diene of 1,2 or 3,4 configuration, the group consisting of units of the 1,3-diene of 1,2 configuration and units of the 1,3-diene of 3,4 configuration representing more than 50 mol % of the units of the 1,3-diene.

Embodiment 10: Copolymer according to any one of embodiments 1 to 9, in which the symbol R represents an aliphatic chain.

Embodiment 11: Copolymer according to any one of embodiments 1 to 10, in which the symbol R represents a hydrocarbon chain having from 6 to 16 carbon atoms.

Embodiment 12: Copolymer according to any one of embodiments 1 to 11, in which the symbol R represents an acyclic chain.

Embodiment 13: Copolymer according to any one of embodiments 1 to 12, in which the symbol R represents a linear or branched chain.

Embodiment 14: Copolymer according to any one of embodiments 1 to 13, in which the 1,3-diene is myrcene or β-farnesene.

Embodiment 15: Copolymer according to any one of embodiments 1 to 14, which copolymer has a glass transition temperature below −35° C., preferably between −90° C. and −35° C.

Embodiment 16: Copolymer according to any one of embodiments 1 to 15, in which the amine function is a tertiary amine function.

Embodiment 17: Copolymer according to any one of embodiments 1 to 16, in which the amine function is a tertiary amine function of formula —N(R_(A))₂ in which each R_(A) represents an alkyl, preferentially a methyl or an ethyl.

Embodiment 18: Copolymer according to any one of embodiments 1 to 17, which copolymer further bears a second function other than an amine function.

Embodiment 19: Copolymer according to embodiment 18, in which the second function borne by the copolymer is a silanol function or an alkoxysilane function.

Embodiment 20: Rubber composition which comprises a copolymer defined according to any one of embodiments 1 to 19, a reinforcing filler and a crosslinking system, which copolymer is an elastomer.

Embodiment 21: Rubber composition according to embodiment 20, in which the reinforcing filler comprises a carbon black.

Embodiment 22: Rubber composition according to embodiment 20 or 21, in which the reinforcing filler comprises a silica.

Embodiment 23: Rubber composition according to any one of embodiments 20 to 22, in which the reinforcing filler comprises a carbon black and a silica.

Embodiment 24: Rubber composition according to any one of embodiments 20 to 23, in which the crosslinking system is a vulcanization system.

Embodiment 25: Tyre which comprises a rubber composition defined according to any one of embodiments 20 to 24.

Embodiment 26: Process for preparing a copolymer defined according to any one of embodiments 1 to 19, which process comprises the following steps:

a) the copolymerization of ethylene and of a 1,3-diene of formula (I) in the presence of a catalytic system comprising a metallocene of formula (II) and an organomagnesium compound of formula (III)

CH₂═CR—CH═CH₂  (I),

P(Cp¹Cp²)Nd(BH₄)_((1+y))L_(y)-N_(x)  (II)

MgR¹R²  (III)

the symbol R representing a hydrocarbon chain having from 3 to 20 carbon atoms,

Cp¹ and Cp², which may be identical or different, being selected from the group consisting of the cyclopentadienyl group of formula C₅H₄, the unsubstituted fluorenyl group of formula C₁₃H₈ and substituted fluorenyl groups,

P being a group bridging the two Cp¹ and Cp² groups and representing a ZR³R⁴ group, Z representing a silicon or carbon atom, R³ and R⁴, which are identical or different, each representing an alkyl group comprising from 1 to 20 carbon atoms, preferably a methyl,

y, which is an integer, being equal to or greater than 0,

x, which is or is not an integer, being equal to or greater than 0,

L representing an alkali metal selected from the group consisting of lithium, sodium and potassium,

N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran,

R¹ and R², which may be identical or different, representing a carbon group, b) the reaction of a functionalizing agent, compound of formula (IV), with the copolymer obtained in step a),

Si(Fc¹)_(3-g)(Rc²)_(g)(Rca)  (IV)

the Fc¹ symbols, which may be identical or different, representing an alkoxy group or a halogen atom,

the Rc² symbols, which may be identical or different, representing a hydrogen atom or a hydrocarbon chain,

the Rca symbol representing a hydrocarbon chain substituted by an amine function,

g being an integer ranging from 0 to 1,

c) where appropriate, a hydrolysis reaction.

Embodiment 27: Process according to embodiment 26, in which P denotes the SiMe₂ group.

Embodiment 28: Process according to either one of embodiments 26 and 27, in which Cp¹ and Cp¹, which may be identical or different, are selected from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C₁₃H₁₈.

Embodiment 29: Process according to any one of embodiments 26 to 28, in which the metallocene catalyst is of formula [{Me₂SiFlu₂Nd(μ-BH₄)₂Li(THF)}₂], [Me₂SiFlu₂Nd(μ-BH₄)₂Li(THF)], [Me₂SiFlu₂Nd(μ-BH₄)(THF)], [{Me₂SiFlu₂Nd(μ-BH₄)(THF)}₂] or [Me₂SiFlu₂Nd(μ-BH₄)], the symbol Flu representing the fluorenyl group of formula C₁₃H₁₈.

Embodiment 30: Process according to any one of embodiments 26 to 29, in which the organomagnesium compound is a dialkylmagnesium compound, preferentially butyloctylmagnesium.

Embodiment 31: Process according to any one of embodiments 26 to 30, in which the functionalizing agent contains at least one Fc¹ symbol.

Embodiment 32: Process according to any one of embodiments 26 to 31, in which the functionalizing agent contains at least two Fc¹ symbols.

Embodiment 33: Process according to any one of embodiments 26 to 32, in which the functionalizing agent contains at least three Fc¹ symbols.

Embodiment 34: Process according to any one of embodiments 26 to 33, in which the alkoxy group represented by an Fc¹ symbol is a methoxy or an ethoxy, preferably a methoxy.

Embodiment 35: Process according to any one of embodiments 26 to 34, in which the Rc² symbols represent an alkyl having at most 6 carbon atoms, preferably methyl or ethyl.

Embodiment 36: Process according to any one of embodiments 26 to 35, in which the hydrocarbon chains denoted in the Rca symbol in formulae (IV), (IV-1), (IV-2), (IV-3) are alkanediyl chains comprising preferably at most 6 carbon atoms, such as the 1,3-propanediyl group.

Embodiment 37: Process according to any one of embodiments 26 to 36, in which the amine function denoted in the Rca symbol is a primary amine function protected by a protecting group, a secondary amine function protected by a protecting group or a tertiary amine function.

Embodiment 38: Process according to embodiment 37, in which the protecting group is a trimethylsilyl or tert-butyldimethylsilyl group.

Embodiment 39: Process according to any one of embodiments 26 to 38, in which the functionalizing agent is (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)methyldiethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldiethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N,N-dimethylaminopropyl)triethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, (N-(3-triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, preferably (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, more preferentially (N,N-dimethylaminopropyl)trimethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine.

The abovementioned characteristics of the present invention, and also others, will be better understood on reading the following description of several exemplary embodiments of the invention, given by way of illustration and without limitation.

Example

1) Determination of the Microstructure of the Polymers:

The spectral characterization and the measurements of the microstructure of copolymer of ethylene and of the 1,3-diene (myrcene) are carried out by nuclear magnetic resonance (NMR) spectroscopy.

Spectrometer: For these measurements, a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe.

Experiments: The ¹H experiments are recorded using a radiofrequency pulse with a tilt angle of 30°, the number of repetitions is 128 with a recycle delay of 5 seconds. The HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation)¹H-¹³C NMR correlation experiments are recorded with a number of repetitions of 128 and a number of increments of 128. The experiments are carried out at 25° C.

Sample preparation: 25 mg of sample are dissolved in 1 ml of deuterated chloroform (CDCl₃).

Sample calibration: The axes of the ¹H and ¹³C chemical shifts are calibrated with respect to the protonated impurity of the solvent (CHCl₃) at δ_(1H)=7.2 ppm and δ_(13C)=77 ppm.

Spectral assignment: The signals of the insertion forms of the 1,3-diene A, B and C (Scheme 1) were observed on the different spectra recorded. According to S. Georges et al. (S. Georges, M. Bria, P. Zinck and M. Visseaux, Polymer, 55 (2014), 3869-3878), the signal of the —CH═ group No. 8″ characteristic of the form C exhibits ¹H and ¹³C chemical shifts identical to the —CH═ group No. 3.

The chemical shifts of the signals characteristic of the moieties A, B and C are presented in Table 1. The moieties A, B and C correspond respectively to the units of 3,4 configuration, of 1,2 configuration and of trans-1,4 configuration.

TABLE 1 Table 1: Assignment of the ¹H and ¹³C signals of Ethylene/Myrcene copolymers δ_(1H) (ppm) δ_(13C) (ppm) Group 5.54 146.4  8′ 5.07 124.6 3 + 8″ 4.97-4.79 112.0  9′ 4.67 108.5 7 2.06 26.5 4  2.0-1.79 31.8 5 + 5′ + 5″ 44.5 8 1.59 25.9 and 17.0 1 1.2  36.8-24.0 CH₂ ethylene

2) Determination of the Functionalization of the Polymers:

The functionalization products of the copolymers are characterized by ¹H, ¹³C, ²⁹Si NMR spectrometry. The NMR spectra are recorded on a Bruker Avance III 500 MHz spectrometer equipped with a BBFO z-grad 5 mm “broad band” cryoprobe. The quantitative ¹H NMR experiment uses a 30° single pulse sequence and a repetition delay of 5 seconds between each acquisition. 64 to 256 accumulations are carried out. The quantitative ¹³C NMR experiment uses a 30° single pulse sequence with a proton decoupling and a repetition delay of 10 seconds between each acquisition. 1024 to 10240 accumulations are carried out. Two-dimensional ¹H/¹³C and ¹H/²⁹Si experiments are used with the aim of determining the structure of the functional polymers. The axis of the ¹H chemical shifts is calibrated with respect to the protonated impurity of the solvent (CDCl₃) at δ_(1H)=7.20 ppm. The axis of the ¹³C chemical shifts is calibrated with respect to the signal of the solvent (CDCl₃) at δ_(13C)=77 ppm. The axis of the ²⁹Si chemical shifts is calibrated with respect to the signal of the TMS at 0 ppm (addition of a few microlitres of TMS to the NMR tube).

The final chemical structure of each functional polymer is identified by ¹H, ¹³C and ²⁹Si NMR.

The 1D ¹H NMR spectrum recorded under quantitative conditions makes it possible to calculate the content of (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane grafted to the polymer. The signals of the protons characteristic of the grafted function are observable at chemical shifts of 3.37 ppm for the methoxy group (CH3-O—Si), 0.11 ppm to 0.02 ppm for the methyl groups bonded to the silicon ((CH3)2-Si) and 0.66 ppm to 0.45 ppm for the methylene unit in the alpha position with regard to the silicon (Si—CH2-R). The grafting structure is confirmed by a two-dimensional proton/silicon-29 correlation map. The silicon signals of the (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane grafted to the polymer at the chain end correspond to two broad unresolved peaks with ²⁹Si chemical shifts between 15 ppm and 16 ppm and between 21 ppm and 23 ppm. These broad unresolved peaks correspond respectively to the function bonded to a diene unit and to an ethylene-based unit.

3) Determination of the Glass Transition Temperature of the Polymers:

The glass transition temperature is measured by means of a differential calorimeter (differential scanning calorimeter) according to standard ASTM D3418 (1999).

4) Determination of the Degree of Crystallinity of the Polymers:

Standard ISO 11357-3:2011 is used to determine the temperature and enthalpy of fusion and of crystallization of the polymers used by differential scanning calorimetry (DSC). The reference enthalpy of polyethylene is 277.1 J/g (according to Polymer Handbook, 4th Edition, J. Brandrup, E. H. Immergut and E. A. Grulke, 1999)

5) Size Exclusion Chromatography (SEC):

a) Principle of the Measurement:

Size exclusion chromatography or SEC makes it possible to separate macromolecules in solution according to their size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, the bulkiest being eluted first.

Combined with 3 detectors (3D), a refractometer, a viscometer and a 90° light scattering detector, SEC makes it possible to learn the absolute molar mass distribution of a polymer. The various number-average (Mn) and weight-average (Mw) absolute molar masses and the dispersity (Ð=Mw/Mn) can also be calculated.

b) Preparation of the Polymer:

Each sample is dissolved in tetrahydrofuran (+1 vol % of diisopropylamine+1 vol % of triethylamine), at a concentration of approximately 1 g/l. The solution is then filtered through a filter with a porosity of 0.45 μm before injection.

c) 3D SEC Analysis for the Elastomers of the Invention:

To determine the number-average molar mass (Mn), and where appropriate the weight-average molar mass (Mw) and the dispersity of the constituents which can be used in the compositions in accordance with the invention, the method below is used.

The number-average molar mass (Mn), the weight-average molar mass (Mw) and the dispersity of the constituent to be tested (hereinafter sample) are determined in an absolute manner by triple detection size exclusion chromatography (SEC). Triple detection size exclusion chromatography has the advantage of measuring average molar masses directly without calibration.

The value of the refractive index increment dn/dc of the sample solution is measured online using the area of the peak detected by the RI of the liquid chromatography equipment. To apply this method, it must be verified that 100% of the sample mass is injected and eluted through the column. The area of the RI depends on the concentration of the sample, the constant of the RI detector and the value of dn/dc.

To determine the average molar masses, use is made of the 1 g/I solution prepared and filtered previously, which is injected into the chromatographic system. The apparatus used is a Waters Alliance chromatographic line. The elution solvent is tetrahydrofuran protected from oxidation with 250 ppm of BHT (2,6-di(tert-butyl)-4-hydroxytoluene), the flow rate is 1 ml·min⁻¹, the temperature of the system is 35° C. and the analytical time is 60 min. The columns used are a set of three Agilent columns of PL Gel Mixed B LS trade name. The volume of the sample solution injected is 100 μl. The detection system is composed of a Wyatt differential viscometer of Viscostar II trade name, of a Wyatt differential refractometer of Optilab T-Rex trade name of wavelength 658 nm and of a Wyatt multi-angle static light scattering detector of wavelength 658 nm and of Dawn Heleos 8+ trade name.

For the calculation of the number-average molar masses and the dispersity, the value of the refractive index increment do/dc of the sample solution obtained above is integrated. The software for evaluating the chromatographic data is the Astra system from Wyatt.

d) 3D SEC Analysis for Elastomers not in Accordance with the Invention or Control Elastomers:

The apparatus used is a Waters Alliance chromatograph. The elution solvent is tetrahydrofuran (+1 vol % of diisopropylamine+1 vol % of triethylamine), the flow rate is 0.5 ml/min, and the system temperature is 35° C. Use is made of a set of four Polymer Laboratories columns in series, two with the “Mixed A LS” trade name and two with the “Mixed B LS” trade name.

The volume of the solution of the polymer sample injected is 100 μl. The detection system used is the TDA 302 from Viscotek, it is composed of a differential refractometer, a differential viscometer and a 90° light scattering detector. For these 3 detectors, the wavelength is 670 nm. For the calculation of the average molar masses, the value of the refractive index increment dn/dC of the polymer solution is integrated, said value being defined beforehand in tetrahydrofuran (+1 vol % of diisopropylamine+1 vol % of triethylamine), at 35° C. and 670 nm. The software for evaluating the data is the Omnisec system from Viscotek.

6) Determination of the Stiffness of the (Cured) Rubber Compositions:

The dynamic properties are measured on a viscosity analyser (Metravib VA4000) according to standard ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical test specimen with a thickness of 4 mm and a cross section of 400 mm²), subjected to a simple alternating sinusoidal shear stress, at a frequency of 10 Hz, under standard temperature conditions (23° C.) according to standard ASTM D 1349-99, is recorded. A strain amplitude sweep is performed from 0.1% to 100% (outward cycle), and then from 100% to 0.1% (return cycle). The results made use of are the complex dynamic shear modulus (G*).

The stiffness results are expressed in base 100 relative to a control taken as reference. A value of less than 100 indicates a value lower than that of the control.

7) Syntheses of the Polymers:

In the synthesis of copolymers in accordance with the invention, the 1,3-diene used (myrcene) is a 1,3-diene of formula (I) in which R is a hydrocarbon group having 6 carbon atoms of formula CH₂—CH₂—CH═CMe₂.

All the reactants are obtained commercially except for the metallocene {Me₂SiFlu₂Nd(μ-BH₄)₂Li(THF)}], which is prepared according to the procedure described in patent application WO 2007054224.

The butyloctylmagnesium BOMAG (20% in heptane, at 0.88 mol·l⁻¹) originates from Chemtura and is stored in a Schlenk tube under an inert atmosphere. The ethylene, of N35 grade, originates from Air Liquide and is used without prepurification. The myrcene (purity≥95%) is obtained from Sigma-Aldrich. The (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane is obtained from ABCR.

Polymerization Procedure:

The cocatalyst, the butyloctylmagnesium (BOMAG) and then the metallocene [Me₂Si(Flu)₂Nd(μ-BH₄)₂Li(THF)] are added to a reactor containing methylcyclohexane. The alkylation time is 10 minutes and the reaction temperature is 20° C. The respective amounts of the constituents of the catalytic system appear in Table 2. The monomers are then added continuously in the respective amounts shown in Table 2. The polymerization is carried out under conditions of constant temperature and pressure given in Table 2. The polymerization reaction is stopped by cooling, degassing of the reactor and addition of ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered by drying in an oven under vacuum to constant mass.

Functionalization Procedure:

When the desired monomer conversion is achieved, the content of the reactor is degassed and then the functionalizing agent, (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, is introduced under an inert atmosphere by excess pressure. The reaction medium is stirred for a time and temperature which are indicated in Table 3. After reaction, the medium is degassed and then precipitated from methanol. The copolymer is recovered by precipitation from methanol, then dried at 60° C. under vacuum to constant mass. The microstructure and the function content of the elastomer are shown in Table 4, the other characteristics of the elastomer are shown in Table 5.

8) Preparation of the Rubber Compositions:

Rubber compositions, of which the formulation expressed in phr (parts by weight per hundred parts of elastomer) appears in Table 6, were prepared according to the following procedure: the copolymer, the silica, and also the various other ingredients, with the exception of the vulcanization system, are successively introduced into an internal mixer (final degree of filling: approximately 70% by volume), the initial vessel temperature of which is approximately 80° C. Thermomechanical working (non-productive phase) is then carried out in one step, which lasts in total approximately 5 min, until a maximum “dropping” temperature of 150° C. is reached. The mixture thus obtained is recovered and cooled and then sulfur and the accelerator are incorporated on a mixer (homofinisher) at 40° C., everything being mixed (productive phase) for approximately ten minutes. The compositions thus obtained are subsequently calendered, either in the form of slabs (thickness of 2 to 3 mm) or of thin sheets of rubber for the measurement of their physical or mechanical properties.

9) Results:

Elastomers CE1 and CE2 are elastomers not in accordance with the invention, elastomers E1 to E3 are elastomers in accordance with the invention.

The properties of the polymers are shown in Table 4. The stiffness values of the compositions are shown in Table 7.

Elastomers E1, E2 and E3 exhibit a degree of crystallinity close to zero and much lower than that of elastomer CE1.

The results relating to the rubber compositions show that elastomer E3 has the property of giving a rubber composition reinforced with a carbon black a much lower stiffness than that imparted by elastomer CE2.

These results on the crystallinity of the elastomers and on the stiffness of the rubber compositions are obtained even though the elastomers have very similar contents of ethylene units.

TABLE 2 Ethylene/Diene Metallocene Cocatalyst ratio Pressure Temperature Ex (mol/L) (mol/L) (mol/mol) (bar) (° C.) CE1 0.00015 0.00075 80/20 4 80 CE2 0.00007 0.0004 80/20 8 80 E1 0.00015 0.00078 70/30 4 80 E2 0.00015 0.00078 70/30 4 60 E3 0.00004 0.0002 65/35 8 70

TABLE 3 Functionalizing agent/cocatalyst Functionalization ratio time Functionalization Ex (mol/mol) (min) temperature (° C.) CE1 2 15 80 CE2 4 15 80 E1 4 60 80 E2 4 60 60 E3 4 15 70

TABLE 4 Function 1,2- content Eth 1,2 Unit 3,4 Unit 1,4 Unit Cyclohexanediyl (per polymer Ex (mol %) diene (mol %) (mol %) (mol %) (mol %) chain) CE1 76.7 Bde 6 — 5.4 11.9 33% CE2 76.7 Bde 9 — 5.6 8.7 35% E1 75.0 Myr 1 15 8 — 28% E2 75.0 Myr 1 15 7 — 45% E3 76.0 Myr 1 16 7 — 35% Eth: ethylene; Bde: 1,3-butadiene, Myr: myrcene.

TABLE 5 M_(n) Ex (g/mol) Tg (° C.) Crystallinity CE1 30100 −38 2.1 CE2 139400 −39 2.8 E1 37100 −64 0.2% E2 47600 −64 0.2% E3 247200 −63 0.2%

TABLE 6 Composition C1 C2 Elastomer CE2 100 0 Elastomer E3 0 100 Carbon black (1) 47 47 Antioxidant (2) 3 3 Anti-ozonant wax 1 1 Stearic acid (3) 2 2 ZnO (4) 3 3 Accelerator (5) 0.6 0.6 Sulfur 1.5 1.5 (1) N375 (2) Mixture, in a 2/1 weight ratio, of N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine (“Santoflex 6-PPD” from Flexsys) and of 2,2,4-trimethyl-1,2-dihydroquinoline (3) Stearin, Pristerene 4931 from Uniquema (4) Zinc oxide, industrial grade from Umicore (5) N-Cyclohexyl-2-benzothiazolesulfenamide (Santocure CBS from Flexsys)

TABLE 7 Composition C1 C2 Stiffness 100 64 

1. Copolymer of ethylene and of a 1,3-diene of formula (I), which copolymer bears an amine function, CH₂═CR—CH═CH₂  (I) the symbol R representing a hydrocarbon chain having from 3 to 20 carbon atoms.
 2. Copolymer according to claim 1, which copolymer contains more than 50 mol % of ethylene units, preferentially at least 60 mol % of ethylene units, more preferentially at least 70 mol % of ethylene units.
 3. Copolymer according to either one of claims 1 and 2, which copolymer contains at most 90 mol % of ethylene units, preferably at most 85 mol % of ethylene units.
 4. Copolymer according to any one of claims 1 to 3, which copolymer contains units of the 1,3-diene of 1,2 or 3,4 configuration, the group consisting of units of the 1,3-diene of 1,2 configuration and units of the 1,3-diene of 3,4 configuration representing more than 50 mol % of the units of the 1,3-diene.
 5. Copolymer according to any one of claims 1 to 4, in which the symbol R represents an aliphatic hydrocarbon chain having from 6 to 16 carbon atoms.
 6. Copolymer according to any one of claims 1 to 5, in which the symbol R represents an acyclic chain.
 7. Copolymer according to any one of claims 1 to 6, in which the 1,3-diene is myrcene or β-farnesene.
 8. Copolymer according to any one of claims 1 to 7, which copolymer has a glass transition temperature below −35° C., preferably between −90° C. and −35° C.
 9. Copolymer according to any one of claims 1 to 8, in which the amine function is at the chain end of the copolymer.
 10. Copolymer according to any one of claims 1 to 9, which copolymer further bears a second function other than an amine function, preferably a silanol function or an alkoxysilane function.
 11. Rubber composition which comprises a copolymer defined according to any one of claims 1 to 10, a reinforcing filler and a crosslinking system, which copolymer is an elastomer.
 12. Rubber composition according to claim 11, in which the reinforcing filler comprises a carbon black or a silica or else a carbon black and a silica.
 13. Tyre which comprises a rubber composition defined according to claim 11 or
 12. 14. Process for preparing a copolymer defined according to any one of claims 1 to 10, which process comprises the following steps: (a) the copolymerization of ethylene and of a 1,3-diene of formula (I) in the presence of a catalytic system comprising a metallocene of formula (II) and an organomagnesium compound of formula (III) CH₂═CR—CH═CH₂  (I) P(Cp¹Cp²)Nd(BH₄)_((1+y))L_(y)-N_(x)  (II) MgR¹R²  (III) the symbol R representing a hydrocarbon chain having from 3 to 20 carbon atoms, Cp¹ and Cp², which may be identical or different, being selected from the group consisting of the cyclopentadienyl group of formula C₅H₄, the unsubstituted fluorenyl group of formula C₁₃H₈ and substituted fluorenyl groups, P being a group bridging the two Cp¹ and Cp² groups and representing a ZR³R⁴ group, Z representing a silicon or carbon atom, R³ and R⁴, which are identical or different, each representing an alkyl group comprising from 1 to 20 carbon atoms, preferably a methyl, y, which is an integer, being equal to or greater than 0, x, which may or may not be an integer, being equal to or greater than 0, L representing an alkali metal selected from the group consisting of lithium, sodium and potassium, N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran, R¹ and R², which may be identical or different, representing a carbon group, (b) the reaction of a functionalizing agent, compound of formula (IV), with the copolymer obtained in step a), Si(Fc¹)_(3-g)(Rc²)_(g)(Rca)  (IV) the Fc¹ symbols, which may be identical or different, representing an alkoxy group or a halogen atom, the Rc² symbols, which may be identical or different, representing a hydrogen atom or a hydrocarbon chain, the Rca symbol representing a hydrocarbon chain substituted by an amine function, g being an integer ranging from 0 to 1, (c) where appropriate, a hydrolysis reaction.
 15. Process according to claim 14, in which the functionalizing agent is (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)methyldiethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldiethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N,N-dimethylaminopropyl)triethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, (N-(3-triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, preferably (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, more preferentially (N,N-dimethylaminopropyl)trimethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silanamine. 